Certain oxyalkylated blown oils and method of making same



Patented June 6, 1950 CERTAIN OXYALKYLATED BLOWN OILS AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser,

Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing.

Original application March 11,

1948, Serial No. 14,398. Divided and this application February 18, 1949, Serial No. 77,294

6 Claims.

The present invention relates to new chemical products or compounds and to the manufacture of same, our present application being a division of our co-pending application Serial No. 14,398, filed March 11, 1948, now Patent No. 2,472,574.

One object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions, and which is also capable of various other uses.

Another object of our invention is to provide a practicable method for manufacturing said new chemical product or compound.

The new chemical compounds herein described are obtained by a succession of three steps:

, (a) Oiticica oil is mixed with raw castor oil and subjected to heating in the presence of an acid catalyst. This particular step results in a series of reactions which may be indicated briefly as follows: (1) dehydration of castor oil; (2) isomerization of the dehydrated castor oil; (3) co-polymerization of the dehydrated or dehydrated isomerized castor oil with the oiticica oil;

(1)) Such product is blown so as to increase the viscosity substantially, but in any event, so as to stay below the gellation point; and

Such bodied or blown vegetable oil product is then subjected to oxyalkylation, particularly oxyethylation, so as to give it distinctly hydrophile properties.

In order that the invention may be completely understood, we will describe the successive steps, although it is understood that the preparation of the intermediate prior to oxidation or air-- blowing, is well known and has been described elsewhere. See U. S. Patent No. 2,318,304, dated May 4, 1943, to Gardner.

The conventional dehydration of castor oil or ricinoleic acid, or some other ester, results in the formation of a diene acid, with the probability that two reactions ordinarily go to approximately the same degree. These reactions may be illustrated in the following manner:

(9,12-linoleic acid),

2 REACTION 2 CH3(OHz)4 (9,11-1inoleic acid) United States patents which illustrate this procedure, are the following: No. 2,140,271, dated Dec. 13, 1938, Schwarcman;2,195,225, Mar. 26, 1940, Priester; 2, 09,065, July 23, 1940, Pelikan; 2,212,385, Aug. 30, 1940, Brod; 2,226,830, Dec. 31, 1940, Priester; 2,226,831, Dec. 31, 1940, Priester; 2,261,663, Nov. 4, 1941, Rheineck; 2,336,186, Dec. '7, 1940, Nessler; 2,351,444, June 13, 1944, Miller; and 2,246,768, June 24, 1941, Ubben.

The mixed isomers maybe treated so as to convert the unconjugated isomer into the conjugated isomer. This isomerization reaction may be indicated thus:

HHHHH (9,12-linoleic acid) (9,11-linoleic acid) U. S. patents exemplifying isomerization procedure of the kind indicated are the following:

No. 2,185,414, dated Jan. 2, 1940, McKinney;

2,242,230, May 20, 1941, Burr; and 2,350,583, June 6, 1944,, Bradley.

As is well known, oiticica oil consists essentially of the glyceride of licanicacid. This is the only known naturally occurring fattyacid which contains a keto group. In addition to the keto group attached to the fourth carbon atom, it contains three conjugated double bonds in the same position as'in eleostearic acid. Insofar that oiticica oil alone polymerizes in the presence of an acid catalyst and so does dehydrated castor oil, it is purely a matter of speculation as to the nature of the complex copolymers obtained in the manner previously described.

OI'I'ICICA OIL-CASTOR OIL CONDENSATE Example 1 500 parts, lay-weight. of raw-castor oiland 500 parts, byweight, of raw oiticica bil were'iplaced in a vessel, and there was added 2 to 10 parts, by weight, of an acid substance such as sodium acid sulfate (NEHSOI!) as activating agent. The

mixture was progressively heated. At 100 C. some indication of moisture evo1ution-was indicated, but at approximately -150 ..:C:..there:-was.:a violent ebullition, and waterewasrexpelled. Apparently, at this point of the. reaction, .a combination occurred between the nascently dehydroxylated castor oil and the dehydrated .oiticica oil. By continuing the reactioniup to .'about='2-50 (7., water was expelled to the amount of about 25 parts, by weight, or more. At a temperature of about 280 C., the reaction apparently-was complete, no more water being given ofi. At this point the composition.":hadibecome very viscous, apparently due to the reaction between the two oils.

OITICICA OIL-CASTOR OILCoNnENsA'rE Example 2 1000 parts, by weight, 'of raw castor oil was treat'e'd' withf-rcm 2* to--10;-=parts,*by weight, of an acidic substance such as sodium acid sulfate.- The process of dehydroxylation was carried on, with progressivenheating,:until a temperature of approximately 250 C. was reached, at which fpoint' therehacf'been "distilled off" approximately -4%-0f water. 1000-'parts3 by weight; of o'iticica oil was then introducedf-the temperature dropiping to about 150"- C. The temperature ofthe mixture' was then gradually brought up to- 280 0.; during which interval "there was a"' further evolution of water- -usually in the neighborhood;

' oi -2%. -Apparen'tly intensereactions occurred during this-period; as the composition became "very viscous. It 's' believed'that a condensation between the dehydroxylated'molecule of the castor oil and the ketonic group'bf the oiticica' oil oc-..

curred. At a temperature of 280C; "the reaction apparently was complete, and the composition was allowed to cool.

OITICICA OIL-CAs'roR OIL CONDENSATE :FEwampZeEJ3 500 grams of rawioiticica oil and 500 grams of acommerciarcastornilwereplaced in aflask along with 10 grams' 'of sodium acid sulfate crystals,

(NQIHSO4.H2O). The mixture was stirred, using a condenser and conventional trap. Using this particular procedure, there was no violent evolutionof watery-and "the first"ndtice'able amount bfw'ater which came "over" was at approximatelyu I80"C. *R-eaction temperature was'fallowed to rise to. 250"C. T-he total amount ofwater 'which came over was approximately-1&5- grams, or s1i'ghtly :more," but in any eVent; less than the expected amount of 25 grams. There also;v

obtain-ed about3'tO FgIamS Ofan oily substance. The resultant: product was .aszde'ep amberi-colore'd, vi'scous oil.

- I'QITICICA' OimCAs'ron 2011. GONDENSATE ."Example' 4 The 'same -procedure was" followedas in the preceding example; exce'pfithatfused sodium-acid sulfate was employed. INaI-ISOi). The amount' employed was 5 grams. In this instance, water did not start to come off until 200 C. was reached. The temperature was allowed to rise to 280 C. when heating was stopped. The total amount 5 of water obtained in this =instance'was 12 grams and the amount of oil obtained was 8 grams.

As stated in the aforementioned U. S. Patent "No. 2,313,304, dated May 4, 1943, to Gardner, the course o'f'the'rea'otion involved in the above ex- 10'-'amples:is not: substantially altered by the substitutionof another. acid sulfate, e. g., potassium acid sulfate; for the catalytically-acting sodium r acid-tsulfate, the ---HSO4 group being the acitivating' agent.

Attention is directed to the fact that one can v:dehydrate the castor oil separately and then mix 'suchdehydrated castor oil with oiticica oil and producethe ultimate condensate in the presence of :the same acid catalyst used for the dehydration of castor oil, or with a further addition of cata Idyst. .-F!or. convenience, howeven-we prefento proeceediin themianner exemplified-in the condensate Examples-1, 3; and 4,=ra-ther than-in the manner y= exemplified'by-Example2.

the .examples which' have 'appeared'immedieately :pneceding v:in Tthe'iteXtf-{the ratio of the two oils; oiticica. on the: one ha-nd;.= and--either castor "-oil oridehydrated""castor oil on the other hand,

is? in iiequal .amountsf by weight. I-Iowever, 'if

desired, for each I OO'partSiiby"weight,of oitici'ca 011,OIIS I'IIPLV'US'fIOIIi 50 to250 parts,'iby weight, of castor oil ordehydrated castor oil.

Having obtained a condensate or co-polymer in the manner described and exemplifiedby the previous examples, thenext step is'subjecting such aproduct to blowing or oxidation with a "gaseous--medium inthe manner commonly employedin'bmwing castor oil or dehydrated castor 011. I It is' well known that oxidized oils can be "obtained from castor oil, ricinoleic acid and variousderivatives of ricinoleic' acid, such as monori'cinolein, .diricinolein, and'polyricinoleic acids. are, produced by the, common practice of "blowing or oxidizing 'castor oil and similar fatty "oils or acids. particularly non-drying unsaturated fatty .oils,"'by means of a'gaseous medium, such as ir, oxygen/ozone, or 'ozonizedair. The gaseous medium, such as air, may be moist or, dry and the oxidation"maytake place in; the presence .or absence. of,.a catalyst. .The, catalyst may be of ,a metallic ,type, such-lasllead,'ricinoleate, cobalt Ilrieincleate, manganese 'ricinoleata, etc.; or it-may be ofgthe, organic type. which. produces peroxide,

. suchas alpha-pinene,linseed oil, etc. Oxidation .:.may take place atatmos'phe'ricpressure. or-superatmospheric pressure, '.i. ..e.,...pressures up .to' or including. 200.v poundsagauge :pressure, and. at any temperature slightly-aboverthe. boiling-.point of ..water., for instance, 1209. C..up: to any temperature v.whichxlo'es not produce unduedecomposition -by pyrol-ytic reaction.

The time of .blowing. may...be. far ly .brief, .for example, 8-10 hours; orit may be quite extensive, for instance, aslong as '101214 days, the longer time periods being employed generally when the temperature isjust slightly above the boiling point of water,-and'when oxidation is with air at atmospheric pressure.

One method of-preparing drastically-oxidized castor oil is described in U. S. Patent No. 2,023,979,

dated Decemberf'l0,;-1935,' to stehr. Also see U. S. Patent No. 2,183,487, dated December 12, 1939, to Colbeth.

Thus, the same conventional procedure orprocedures employed for oxidation of castor oil or similar compounds, is equally suitable for the blowing or oxidation of oiticica oil-castor oil condensate or polymer, as previously described. In most instances, the period of oxidation may be somewhat longer, although it is also possible to obtain satisfactory products, in which the period of oxidation is somewhat reduced in comparison with the oxidation of castor oil or triricinolein under the same conditions. The application of oxidation is so similar to or identical with that of castor oil, that any difierences of manipulation which may be required are perfectly apparent in the ordinary conduct of theprocess. For instance, if one attempts to oxidize oiticica oil-castor oil condensate or polymer, as herein described, to obtain the same viscosity as an oxidized castor oil, and if at the end of the predetermined period, the viscosity or other index indicates under-oxidation, naturally, the process is continued until the same or a comparable degree of oxidation is obtained. Similarly, in the conventional blowing of castor oil, the last stage of oxidation is somewhat critical and sometimes the period of blowing must be shortened. If, durin the oxidation of hydroxy-acetylated castor oil, there happens to be an increased or intensive period of reaction, obviously only the ordinary precautions need be taken to prevent over-oxidation. The degree of oxidation can be measured, or at least approximated, by the percentage reduction in iodine value, simultaneously with the increase in viscosity.

OXIDIZED OITICICA OIL-CASTOR OIL CONDENSATE Example 1 The 1000 gram sample obtained in the manner described under the heading Oiticica oil-castor L even 2. deeper amber 00101 and was GVEI]. more.

viscous. The viscosity was so high it became apparent that any further oxidation would lead to incipient gellation.

Oxrmzsn OITICICA OIL-CASTOR OIL CONDENSATE Example 2 The same procedure was repeated as in the preceding example, except that the condensate subjected to oxidation was the one described under the heading Oiticica oil-castor oil condensate, Example 4 instead of the one employed in the previous example, to wit, oiticica oil-castor oil condensate, Example 2. The temperature and the time required were identical as in the preceding example, and air was passed through in a slow stream. The appearance of the final product was substantially the same as the appearance of the product in the example immediately preceding.

Having obtained the oxidized oiticica oil-castor oil condensate in the manner exemplified by the two preceding examples, the next step is to subject such a product to oxyalkylation with an alkylene oxide. Suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, glycide, and methyl glycide.

OxYALKYLA'rEn OXIDIZED OrrroIoA OIL-CAS'I'OR OIL CONDENSATE a Example 1 The 1000 gram sample of oxidized oiticica oilcastor oil condensate described under the heading Oxidized oiticica oil-castor oil condensate, Example 1, was mixed with 18 grams of sodium methylate and placed in an autoclave equipped with a stirring device and a heating device. 400 grams of ethylene oxide was added and the product stirred for ten hours. It will be noted that a small amount of the sodium methylate was used up in neutralizing the acid catalyst which remained as a result of the condensate reaction, but the bulk of the sodium methylate was present as a catalyst to accelerate the reaction with the alkylene oxide. During the first stage of oxyalkylation, the time required was approximately four hours. The temperature during this period was to C. The maximum gauge pressure was approximately 'pounds per square inch. At the end of the first addition of ethylene oxide, the product was somewhat reduced in viscosity, there was a slight decrease in, color, and the product showed a tendency to emulsify in the water.

A second addition of ethylene oxide was made in the same amount as before, to wit, 400 grams. The time, temperature, and pressure were substantially identical, as with the initial addition. The product obtained was less viscous than before, lighter in color, and emulsified readily and showed a distinct tendency towards solubility.

A third addition of ethylene oxide was made the same as before. The amount added was 400 grams. The time, temperature, and maximum pressure during oxyalkylation was substantially the same as in the preceding two stages. The final product obtained was a non-viscous liquid, much lighter in color than the original sample and very readily water-soluble. It was to be noted that this material contained no diluent.

OXYALKYLATED Oxrmzxo Orriorczx OIL-CASTOR OIL CONDENSATE.

OXYALKYLATED OXIDIZED OITICICA OIL-CASTOR OIL CONDENSATE Example 3 The same procedure was followed as in the two preceding examples, except that the oxidizedoiticica oil-castor oil condensate were treated with the same weights of propylene oxide instead of ethylene oxide.

As has been previously pointed out, the alkylene oxides which may be employed include not only those mentioned in the two preceding examples, put also butylene oxide, glycide, and methyl glycide. It is also to be noted that any of the products described at the end of the first stage 7 orsecond stage of alkyl'ationin the three preceding examples, are just as'satisfactory for use as when the entire amount of alkylene oxide is added. All that is required is that the addition of the alk'yleneoxide 'be'suifi'cient to contribute distinct hydrophile properties, i; e., that the resultant obtained from theoxyalky-lation stage or step mixes with water to" give a suspension or is sel f-emulsifiable, or gives a sol or clear-solution. Asa rule, such sols, solutions, or suspensions give avery' definite 'andpermanent foam on shaking.

The'amount of alkylene oxide which may be employed is not limited to the amounts indicated, and if desired, may be two or three times the amounts of'the initial oxidized'c'ondensate.

Materials of the kind herein specified and claimed are-useful as demulsifiers for petroleum emulsions of the water in-oil'type, as wetting, detergent, and leveling a ents" in the laundry, textile, and dyein'g industrie's as wetting agents and'detergents in the acid washing of fruit; in the acid washing of'bu'ilding stone and brick; as a wetting agent and-spreader in'the application of asphalt in'ro'ad' buildingan'd the like; as a constituent of soldering fiux preparations; as a flotation'reagent inthe flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged-particles such as sewage, coal washing waste water, and'various trade wastes, and the like; as germicides, insecticides, emulsifiersior cosmetics; spray oils, water repellent textilefinish, etc. These'usesareby no means exhaustive.

Particular mention is made in respect to the use of these products in the removal of mud sheaths, as described in U. S. Patent No. 2,135,909, dated November 8, 1938, to Louis '1. Monson.

Having thus described'our invention, what we claim as new and desire-t secure by Letters Patent is:

1. An oxyalkylated; drastically-oxidized oiticica oil-castor oi-l condensate, said condensate being obtained by a reaction within the temperature range of 250 C. to about 280 C. in the presence of an acid sulfate activating agent; the propor tion of oiticica oil to castor oil being within the range of one part of castor oil to two parts of oiticica oil, up to five-parts of castor oil to two parts of oiticica oil; said oxidation being by means of a gaseous oxygen-containing medium and said oxyalkylation being sufiicient to endow the final product with distinctly hydrophile properties and with the final proviso that the oxyalkylating agent be selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methyl glycide.

2. The product of claim 1, wherein the mixture of vegetable oils is in substantially equal amounts.

3. The product of claim 1, wherein the mixture of vegetable oils is in substantially equal amounts and the oxyalkylatingagent is ethylene oxide.

4. The product of claim 1, wherein the mixture of vegetable oils is in substantially equal amounts and the oxyalkylating agent is ethylene oxide employed in an amount at least equal to the oxidized condensate.

5-. The product of claim 1, wherein the mixture of vegetable oils is in substantially equal amounts and. the oxyalkylating agent is ethylene oxide employed in an amount at least equal to the oxidized condensate, with the proviso that the castor oil dehydration step and condensation with the oiticica oil take place simultaneously.

6. A method for obtaining a distinctly hydrophile substance, characterized by the following steps: (a) condensing an oiticica oil-castor oil mixture within the temperature range of 250 C. to about 280 C. in the presence of an acid sulfate activating agent, with the proviso that a proportion of the oiticica to castor oil be within the range of one part of castor oil to two parts of oiticica oil, up to five parts of castor oil to two parts of oiticica oil; (b) drastically oxidizing said condensate by means of a gaseous oxygen-containing medium; and (c) oxyalkylating said drastically oxidized condensate by means of an oxyalkylating agent selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methyl glycide, and with the final proviso that the said resultant product be endowed with distinct hydrophile properties.

MELVIN DE GROOTE. BERNHARD KEISER.

No references cited. 

1. AN OXYALKYLATED, DRASTICALLY-OXIDIZED OITICICA OIL-CASTOR OIL CONDENSATE, SAID CONDENSATE BEING OBTAINED BY A REACTION WITHIN THE TEMPERATURE RANGE OF 250*C. TO ABOUT 280*C. IN THE PRESENCE OF AN ACID SULFATE ACTIVATING AGENT; THE PROPORTION OF OITICICA OIL TO CASTOR OIL BEING WITHIN THE RANGE OF ONE PART OF CASTOR OIL TO TWO PARTS OF OITICICA OIL, UP TO FIVE PARTS OF CASTOR OIL TO TWO PARTS OF OITICICA OIL; SAID OXIDATION BEING BY MEANS OF A GASEOUS OXYGEN-CONTAINING MEDIUM AND SAID OXYALKYLATION BEING SUFFICIENT TO ENDOW THE FINAL PRODUCT WITH DISTINCTLY HYDROPHILE PROPERTIES AND WITH THE FINAL PROVISO THAT THE OXYALKYLATING AGENT BE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE, AND METHYL GLYCIDE. 